Garnet-type composite metal oxide particle and method for producing same, and compression-molded product of garnet-type composite metal oxide
View Patent ↗The present disclosure is directed to a composite metal oxide particle, and method of producing the same, having an excellent lithium ion conductivity that may be produced at low cost. The present disclosure relates to a garnet-type composite metal oxide particle, containing Li, La, Zr and O; Ga and/or Al; and a halogen element, where a part of a Li site is substituted with the Ga and/or the Al, and at least a part of a particle surface is covered with a melt-solidified material. A ratio of an area covered with the melt-solidified material to a total area of the particle is preferably 10% or more, and the halogen element is preferably Cl.
1. A composite metal oxide particle comprising:
Li, La, Zr and O;
Ga and/or Al; and
a halogen element,
wherein:
the composite metal oxide has a garnet structure,
a part of an Li site is substituted with the Ga and/or the Al,
at least a part of a particle surface is covered with a melt-solidified material, and
a ratio of A 1 to a total of A 1 and A 2 is 20% or more and 90% or less,
where A 1 is an area of a maximum peak of Li 7 La 3 Zr 2 O 12 substituted with the Ga and/or the Al,
where A 2 is an area of a maximum peak of La 2 O 3 , and
where A 1 and A 2 are obtained by X-ray diffraction analysis.
2. The composite metal oxide particle according to claim 1 , wherein a ratio of an area covered with the melt-solidified material to a total area of the particle is 10% or more.
3. The composite metal oxide particle according to claim 1 , wherein the halogen element is Cl.
4. The composite metal oxide particle according to claim 1 , wherein the melt-solidified material is at least one of a halide and an oxyhalide.
5. A compression-molded product of a composite metal oxide comprising:
Li, La, Zr and O;
Ga and/or Al; and
a halogen element,
wherein a part of an Li site is substituted with the Ga and/or the Al,
wherein the compression-molded product is obtained by compression-molding the particle according to claim 1 , and
wherein the composite metal oxide comprises a pasty structure in a cross-section parallel to a compression direction.
6. The compression-molded product according to claim 5 , wherein a percent area of the pasty structure in a total area of the compression molded product in the cross-section parallel to the compression direction is 10% or more.
7. A solid electrolyte material for a secondary battery comprising the composite metal oxide particle according to claim 1 .
8. The composite metal oxide particle according to claim 1 , wherein the ratio of A 1 to a total of A 1 and A 2 is 20% or more and 50% or less.
9. A composite metal oxide particle comprising:
Li, La, Zr and O;
Ga and/or Al; and
a halogen element,
wherein:
the composite metal oxide has a garnet structure,
at least one of Li, La, Zr, Ga and Al forms an oxyhalide and/or the Li forms a halide, and
a ratio of A 1 to a total of A 1 and A 2 is 20% or more and 90% or less,
where A 1 is an area of a maximum peak of Li 7 La 3 Zr 2 O 12 substituted with the Ga and/or the Al,
where A 2 is an area of a maximum peak of La 2 O 3 , and
where A 1 and A 2 are obtained by X-ray diffraction analysis.
10. A solid electrolyte material for a secondary battery, comprising the composite metal oxide particle according to claim 9 .
11. The composite metal oxide particle according to claim 9 , wherein the ratio of A 1 to a total of A 1 and A 2 is 20% or more and 50% or less.
12. A method for producing the garnet-type composite metal oxide particle according to claim 1 , comprising at least a step of reacting by a mechanochemical method.
13. The method for producing the garnet-type composite metal oxide particle according to claim 12 , wherein a mixture is treated by reacting in the mechanochemical method, wherein the mixture comprises:
an Li source powder,
an La source powder and a Zr source powder;
a Ga source powder and/or an Al source powder; and
a halide of Li.
14. The method for producing the garnet-type composite metal oxide particle according to claim 13 , wherein the halide of Li is LiCl.
15. A method for producing the garnet-type composite metal oxide particle according to claim 9 , comprising at least a step of reacting by a mechanochemical method.
16. The method for producing the garnet-type composite metal oxide particle according to claim 15 , wherein a mixture is treated by reacting in the mechanochemical method, wherein the mixture comprises:
an Li source powder,
an La source powder and a Zr source powder;
a Ga source powder and/or an Al source powder; and
a halide of Li.